Continuous dyeing of polyester fibres with azo dyestuffs soluble in water-immerscible halogenated hydrocarbons

ABSTRACT

Process for the continuous dyeing of synthetic fibre materials from organic solvents wherein the fibre materials are impregnated with dyeing liquors containing azo dyestuffs which are soluble in organic solvents and correspond to the formula   IN WHICH A, R1, R2, R3 and R4 have the meaning given in the disclosure and are subsequently subjected to a heat treatment.

nited States Patent 1191.

Wolfram et a1.

[ Nov. 27, 1973 CONTINUOUS DYEING OF POLYESTER FIBRES WITH AZO DYESTUFFSSOLUBLE IN WATER-IMMIRSCIBLE HALOGENATED HYDROCARBONS [75] lnventors:Gerhard Wolfrum, Opladen; Rutger Neefl; Winiried Kruckenberg, both ofLeverkusen, all of Germany [73] Assignee: Bayer Aktiengesellschaft,

Leverkusen, Germany [22] Filed: Dec. 18, 1970 [21] Appl. No.: 99,719

[30] Foreign Application Priority Data Jan. 2, 1970 Germany P 20 00131.4

52 u.s.c1 ..s/'41 c,8/26,8/82, 8/4] H, 8/41 1), 8/50, 260/158, 260/173,260/174, 260/207.1

Upshur 8/94 X 3,579,497 5/1971 Ramanathan et al...... 8/41 X 3,122,4102/1964 Mueller et a1 8/41 R 3,096,320 7/1963 Lange et a1. 260/1583,057,848 10/1962 Dehn, Jr. et a1. 260/158 FOREIGN PATENTS ORAPPLICATIQNS 1,192,984 5/1970 Great Britain 8/174 1,581,325 9/1969France 832,343 l/l970 Canada Primary Examiner-George F. Lesmes AssistantExaminer-Patricia C. lves Attorney-Plumley & Tyner [5 7] ABSTRACTProcess for the continuous dyeing of synthetic fibre materials fromorganic solvents wherein the fibre materials are impregnated with dyeingliquors containing azo dyestuffs which are soluble in organic solventsand correspond to the formula in which A, R,, R R and R have the meaninggiven in the disclosure and are subsequently subjected to a heattreatment.

15 Claims, No Drawings CONTINUOUS DYEING OF POLYESTER FIBRES WITH AZODYESTUFFS SOLUBLE IN WATER-XMMIRSCIBLE HALOGENATED HYDROCARBONS Theinvention relates to a process for the continuous dyeing of syntheticfibre materials; more particularly it concerns a process for thecontinuous dyeing of synthetic fibre materials from organic solventswherein the fibre materials are impregnated with dyeing liquorscontaining azo dyestuffs which are soluble in organic solvents andcorrespond to the formula R means hydrogen, a chlorine or bromine atom,a

methyl, methoxy or ethoxy group;

R is hydrogen, a chlorine or bromine atom, a methyl,

methoxy, ethoxy group or an acylamino group of the formula -Nl-l-CO-Rwhere R stands for a C,C -alkyl, cycloalkyl, benzyl radical, a phenylradical which may be substituted by C,-C,,-alkyl group or aphenoxymethyl radical, an acyloxymethyl group containing one 18 carbonatoms in the acyl radical, a methoxymethyl, chloromethyl, C C -alkoxygroup or a dialkylamino group containing one 18 carbon atoms;

hexyl, decyl, undecyl, dodecyl, 2,2-dimethyl-decyl, te-

tradecyl, hexadecyl and stearyl radicals and for R as C,- and C -aIkylradicals the methyl and ethyl radicals;

as cycloalkyl radicals, the cyclohexyl, methyl- 5 cyclohexyl and4-tert.-butyl-cyclohexyl radicals; as

aralkyl radicals, in particular, the benzyl or dodecylbenzyl-radical.

For R there may be mentioned as phenyl radicals substituted by C,--C-alkyl groups, for example: the 4-methyl-phenyl, 2,4-dimethyl-phenyl,4-tert.-butylphenyl, 4-nonyl-phenyl, 4-dodecyl-phenyl radicals.

The dyestuffs to be used for dyeing from organic solvents according tothe invention are obtained by known methods, for example, by diazotisingan aromatic carbocyclic or a heterocyclic diazo component of the formulaA-NH and coupling the resultant diazonium salts with compounds of theformula in which R R R and R have the same meaning as in formula (1).Suitable coupling components are primarily those amines of the formula(ll) in which a. R denotes an ethyl group;

R stands for a B-acyl-oxy-ethyl group in which the acyl radical is atern-butyl-earbonyl, pentyl-(3)- carbonyl, heptyl-( 3 )-carbonyl,heptadecylcarbonyl or 4-tert.-butyl-phenyl-carbonyl radical;

R denotes the groupings +C,,H ,,-O+,,,CO-R or R means hydrogen, amethyl, methoxy or ethoxy group; and CH;CH0 CEO-R6 R is hydrogen, achlorine atom, a methyl group or an HPO acylamino group in which theacyl radical is an acetyl, ethoxy-carbonyl, t-butyl-carbonyl,pentyl-(3)- where R stands for a C C preferably C,,C carbonyl,4-tert.-butyl-phenyl-carbonyl or alkyl radical, a cycloalkyl radical, aphenyl radical dibutylamino-carbonyl radical. which may be substitutedby C --C, -alkyl groups, b. or a benzyl or phenoxy methyl radical whichmay R denotes a B-cyanoethyl group; be substituted by C,C -alkyl groups;R stands for a B-acyloxy-ethyl group in which the m means 1 or 2 andacyl radical is a tert.-butyl-carbonyl, i-butyln is l, 2 or 3; andcarbonyl, sec.-butyl-carbonyl or 4-propyl-phenyl- R denotes hydrogen, aC,- C -alkyl radical, a benzyl carbonyl radical;

radical which may be substituted by halogen atoms, R denotes hydrogen, amethyl, methoxy or ethoxy C,C -alkyl or C --C, alkoxy groups, afi-phenylgroup; and ethyl, B-cyanoethyl, fl-methoxyethyl, /3ethox Rmeans hydrogen, a bromine atom, a methyl group yethyl, B-C C-alkylsulphonyl-ethyl, B-phenylor an acylamino group in which the acylradical is sulphonylethyl or fi-vinylsulphonyl ethyl radical, or anethoxycarbonyl, 4-tert.-butyl-phenoxy- R, has the same meaning as Rcarbonyl, tert.-butylcarbonyl, heptadecyl-carbonyl with the proviso thatthe sum total of carbon atoms or phenoxymethyl-carbonyl radical.

contained in the substituents R,, R R and R c. amounts to at least 6 andat most 28, preferably to R denotes a benzyl group; 10 to 20, and thatthe materials are subsequently R stands for a fi-acyloxy-ethyl group inwhich the subjected to a heat treatment. acyl radical is an-butyl-carbonyl, i-amyl-carbonyl, For R and R there may be mentioned byway of exheptadecyl-carbonyl, t-butyl-carbonyl, sec-amylample: carbonylor heptyl-(3)-carb'onyl radical; as C C, -alkyl radicals, the propyl,iso-propyl, n- R, denotes hydrogen, a methyl, methoxy or ethoxy butyl,iso-butyl, sec.-butyl, tert.-butyl, n-pentyl, isogroup; and amyl,sec.-pentyl, neopentyl, n-hexyl, methyl-pentyl, R means hydrogen, achlorine atom, a methyl or medimethyl-butyl, n-heptyl, methyl-hexyl,dimethylthoxy group or an acylamino group in which the pentyl,trimethyl-butyl, n-octyl, iso-octyl, methylacyl radical is a4-methyl-benzoyl, n-butylheptyl, dimethyl-hexyl, trimethyl-pentyl,tetramethylbutyl n-nonyl, iso-nonyl, dimethyl-heptyl, trimethylcarbonyl,heptyl-(3)-carbonyl or benzyl-carbonyl group.

R, denotes a B-phenyl-ethyl group;

R stands for a B-acyloxy-ethyl group in which the acyl radical is abutyryl, i-amyl-carbonyl, t-butylcarbonyl, pentyl-(3)-carbonyl orheptyl-(3)- carbonyl radical;

R denotes hydrogen, a methyl, methoxy or ethoxy group; and

R means hydrogen, a chlorine atom, a methyl group or an acylamino groupin which the acyl radical is an acetyl, 4-t-butyl-benzoyl,t-butyl-carbonyl, cyclohexyl-carbonyl or heptyl-(3)-carbonyl radical.

R and R denote a B-acyloXy-ethyl group in which the acyl radical is abutyryl, t-butyl-'carbonyl, pentyl-(3 )-carbonyl, heptyl-(3)-carbonyl,heptadecyl-carbonyl, 4-t-butyl-benz0yl, benzyl-carbonyl orphenoxymethyl-carbonyl radical;

R denotes hydrogen, a methyl, methoxy or ethoxy group; and

R means hydrogen, a chlorine atom, a methyl or methoxy group or anacylamino group in which the acyl radical is a propionyl,tbutyl-carbonyl, pentyl- (3)-carbonyl, 4-t-butyl-benzoyl,ethoxy-carbonyl,

n-butyoxy-carbonyl, benzoyl, benzyl-carbonyl or phenoXy-methyl-carbonylradical. f.

R denotes group;

R stands for a B-phenylsulphonyl-ethyl, B-vinylsulphonyl-ethyl group ora B-alkylsulphonyl-ethyl group in which the alkyl radical is a methyl,ethyl, butyl or octyl group;

R denotes hydrogen, a methyl, methoxy or ethoxy group; and

R means hydrogen, a chlorine atom, a methyl group or an acylamino groupin which the acyl radical is an acetyl, benzoyl or t-butyl-carbonylradical.

Among the azo dyestuffs to be used according to the invention thosedyestuffs of the formula (I) have proved particularly satisfactory, inwhich A stands for a phenyl radical of the formula a /3-( heptyl-( 3)-carbonyl-oxy)-ethyl (III) in which R denotes a halogen atom, aC,C.,-alkyl, C,-C alkoxy, C,-C -alkoxy-carbonyl, cyclohexoxycarbonyl-,tri-fluoromethyl, nitro, cyano, C,C alkylsulphonyl, phenylsulphonyl or C-C -dialkylamino-sulphonyl group; R means hydrogen, a halogen atom or anitro group;

and R denotes hydrogen, a halogen atom or a cyano group, or for anoptionally substituted thiazole or 6 OzN or for a thiadizole radical ofthe formula in which R denotes a C,C.,-alkyl group or an optionallysubstituted phenyl radical.

Examples of diazo components of the formula A-NH are the followingcompounds: 4-chloro-aniline, 2-chloro-aniline, 4-bromo-anilinc, 4-methyl-aniline, 4-nitro-aniline, 2-nitro-aniline,2-methoxy-4-nitro-aniline, 2-chloro-4-nitro-aniline,4-chloro-2-nitro-aniline, 4-chloro-3-nitro-aniline, 4- cyano-aniline,4-methoxycarbonyl-aniline, 2,4-, 2,5-, 2,6- and 3,4-dichloro-aniline,2,4,5-trichloro-aniline, 2,4,5,6-tetrachloro-aniline,pentachloro-aniline, 2,4- dibromo-aniline, 2-methyl-4-chloro-anilinc, 2-trifluoromethyl-4chloro-aniline, 2-cyano-4-chloroaniline,2-chloro-4-cyano-aniline, 2-cyano-5-chloroaniline,2-cyano-4-nitro-aniline, 2-methoxycarbonyl-4- nitro-aniline,2-methoxycarbonyl-4-chloro-aniline, 2- chloro-4-ethoxycarbonyl-aniline,2-nitro-4-butoxycarbonyl-aniline, 2,4-dinitro-aniline,2,6-dichloro-4-nitroaniline, 2,6-dibromo-4-nitro-aniline, 2,4-dinitro-6-chloroor -6-bromo-aniline, 2,6-dichloro-4-cyanoaniline,2,6-dinitro-4-chloro-aniline, 2-bromo-4-nitro- 6-cyano-aniline,2-chloro-4-nitro-6-cyano-aniline, 4-methylsulphonyl-aniline,2-bromo-4-ethylsulphonylaniline, 2-nitro-4-ethylsulphonyl-aniline,2-bromo-4- ethyl-sulphonyl-6-nitro-aniline, 2,6-dichloro-aniline-4-sulphonic acid diethylamide, 2,5-dichloro-anilinc-4- sulphonic aciddibutylamide, 2 -methoxy-4-nitroaniline, 2,4-dicyano-aniline,3,4-dicyano-anilinc, 2,4-dicyano-6-chloro-aniline,2,6-dicyano-6-nitroaniline, 2,4-dicyano-6-nitro-aniline,S-amino-B-mcthylthiadiazole-( l ,2,4), 5-amino-3-phenyl-thiadiazolc-1,2,4), 5-amino-3-ethylsulphonyl-thiadiazole-( 1,2,4),5-amino-3-benzylmercapto-thiadia2ole-( 1,2,4), 5-nitro-2-amino-thiazole-( l ,3), 2-amino-benzothiazole- 1,32-amino-6-methylsulphonyl-benzothiazole- (1,3),2-amino-6-thiocyano-benzothiazole-(l,3), 2- amino-5-cyano-thiazole-( l,3), thiazole-(1,3), 2-amino-5-nitro-4-methyl-thiazole- (1,3),2-amino-4-phenyl-thiazole-( 1,3), 2-amino-4-(4- chlorophenyl)-thiazole-(1,3), 2-amino-4-(4- nitrophenyl )-thiazole-( l ,3), 2-amino-6-methyl-2-amino-4-methyl-' benzothiazole-( 1 ,3),2-amino-6-methoxybenz'othiazole-( 1 ,3), 2-amino-6-ch1orobenzothiazole-(1,3), 2-amino-6-nitro-benzothiazole-(1,3), 2-amino-1,3-benzothiazole-6-carboxylic acid ethyl ester or butyl ester,2-amino-thiadiazole-( 1,3,4), S-aminothiadiazole-( 1,3,4),3-amino-5-nitro-benzoisothiazole- (2,13-amino-7-bromo-5-nitro-benzoisothiazole- 2,1

Organic solvents suitable for the process according to the invention arethose solvents which are not miscible with water and the boiling pointof which lies between 40 and 150C, for example, aromatic hydrocarbons,such as toluene, xylene; halogenated hydrocarbons, especially aliphaticchlorinated hydrocarbons, such as methylene chloride, chloroform, carbontetrachloride, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2-

trichloroethane, 1,1,l,2-tetrachloro-ethane, 1,1 ,2,2-tetrachloroethane, pentachloroethane, 1- chloropropane,1,2-dichloropropane, 1 ,1,ltrichloropropane, l-chlorobutane,2-chlorobutane,

1,4-dichlorobutane, 1-chloro-2-methyl-propane or2-chloro-2-methyl-propane; as well as aliphatic fluorinated andfluoro-chlorinated hydrocarbons, such as perfluoro-n-hexane, 1,2,2-trifluoro-trichloroethane and 1,1,1-trifluoro-pentachloro-propane;and aromatic chlorinated and fluorinated hydrocarbons, such aschlorobenzene, fluorobenzene, chlorotoluene and benzotrifluoride.Tetrachloroethylene, trichloroethylene and 1,1,1-trichloroethane haveproved particularly sat isfactory.

Furthermore, it has proved advantageous in some cases to add non-ionicauxiliaries to the dyebaths. Suitable non-ionic auxiliaries areprimarily the known interface-active ethoxylation and propoxylationproducts of fatty alcohols, alkylphenols, fatty acid amides and fattyacids, as well as mixtures thereof; the auxiliaries are used in amountsof 0.05 to 2 percent by weight, referred to the weight of the organicsolvents. Instead of adding the auxiliaries directly to the dyebaths,they may also be used with advantage for pasting the dyestuffs and thusbe added to the dyebaths in the form of a dyestuff/auxiliary paste.

The synthetic fibre materials to be dyed according to the process of theinvention are mainly fibre materials of polyesters, for example,polyethylene terephthalates or polyesters from 1 ,4-bis-(hydroxymethylcyclohexane and terephthalic acid; polycarbonates of4,4'-dihydroxy-diphenyl-2,2-propane; cellulose triacetate; syntheticpolyamides, such as poly-e-caprolactam, polyhexamethylene diamineadipate or poly-maminoundecanic acid; polyurethanes or polyolefins. Thefibre material may be present in the form of fabrics and knittedfabrics.

For dyeing, the dyestuffs to be used according to the invention aredissolved in the water-immiscible organic solvents or they are added tothe latter in the form of solutions in solvents of unlimited miscibilitywith these solvents, such as alcohols, dimcthyl formamide, dimethylacetamide, dimethyl sulphoxide or sulpholanc; the synthetic fibrematerials are impregnated with the resultant clear dyestuff solutionswhich may contain soluble non-ionic auxiliaries for improving thelevelness of the dyeings, for example, the known interfaceactiveethoxylation and propoxylation products of fatty alcohols,a1ky1-phenols, fatty acid amides and fatty acids. The dyestuffs aresubsequently fixed on the fibre materials by means of a heat treatment.The heat treatment may consist in a brief treatment with dry heat at 120230C with an intermediate drying possibly preceding the dry heattreatment, or in a treatment of the fibre materials in an overheatedsolvent vapour at 150C. Small proportions of non-fixed dyestuff can bewashed out by a brief treatment with the cold organic solvent. It shouldbe noted that mixtures of the dyestuffs to be used according to theinvention sometimes yield a higher dyestuff yield than the individualdyestuffs and that they may be even more readily soluble in the organicmedium.

With the aid of the process according to the invention it is possible toobtain dyeings characterised by a high dyestuff yield, very goodbuild-up and by outstanding fastness properties, especially very goodfastness to thermo-fixing, washing, rubbing and light, on syntheticfibre materials by dyeing from organic solvents. Another advantage ofthe dyestuffs to be used according to the invention is their highsolubility in organic solvents, especially in water-immiscible solvents,such s tetrachloroethylene, trichloroethylene, 1,1,1- trichloroethaneand 1,1,l-trichloropropane, which enables the dyeingto be carried outwithout the use of solubilizers.

The parts given in the following Examples are parts by weight.

EXAMPLE 1 A fabric of polyethylene terephthalate fibres is impregnatedat room temperature with a clear brown solution containing 10 parts of adyestuff of the formula JENQ N c,11.oco-cmcmcmcm): 1 H3 in 990 partstetrachloroethylene.

After squeezing to a weight increase of 60%, the fabric is dried at 80Cfor 1 minute. The dyestuff is subsequently fixed by heating the fabricat 190 220C for 45 seconds. The small proportion of non-fixed dyestuffis subsequently washed out by a brief treatment in coldtetrachloroethylene for 20 seconds. After drying, a yellow-brown dyeingis obtained, which is characterised by its high dyestuff yield, verygood build-up and outstanding fastness properties, especially very goodfastness to thermofixing, washing, rubbing and light.

7 Clear yellow-brown dyeings of the same quality were obtained in ananalogous manner on fabrics of a. cellulose triacetate b. syntheticpolyamides or polyurethanes, and

c. polypropylene fibres, but thermosolisation was carried out for a. at200 220C h. at 170 200C and c. at C.

Equally satisfactory dyeings were also obtained when the 990 partstetrachloroethylene were replaced with the same amount of one of thefollowing solvents: methylene chloride, chloroform, carbontetrachloride, tetrachloroethane, dichloropropane, l ,1 ,1-trichloropropane, chlorobutane, dichlorobutane.

EXAMPLE 2 A knitted fabric of polyhexamethylene-diamine adipatefilaments is impregnated at room temperature with an orange solutioncontaining 10 parts of a dyestuff of the formula in 990 partstetrachloroethylene.

After squeezing to a weight increase 60%, the knitted fabric is dried at80C for 1 minute. The dyestuff is subsequently fixed by heating theknitted fabric at 192C for 45 seconds. Small proportions of non-fixeddyestuff are then washed out by a brief treatment with coldtetrachloroethylene. After drying, a clear orange dyeing is obtained,which is characterised by its high dyestuff yield, very good build-up,and outstanding fastness properties, especially very good fastness tothermofixing, washing, rubbing and light.

A dyeing of the same quality was obtained when the 990 partstetrachloroethylene were replaced with the same amount of toluene,xylene, chlorobenzene or dichlorobenzene.

EXAMPLE 3 A fabric of polypropylene fibres is impregnated at roomtemperature with a clear yellow solution containing parts of a dyestuffof the formula 7 parts nonylphenyl heptaethylene glycol ether in 983parts tetrachloroethylene. After squeezing to a weight increase ofpercent, the fabric is dried at C for 1 minute. The dyestuff issubsequently fixed by heating the fabric at C for 30 seconds. Anynon-fixed dyestuff particles can be washed out by a brief treatment inthe cold solvent. A clear orange dyeing is obtained, which ischaracterised by its high dyestuff yield, very good build-up andoutstanding fastness properties, especially very good fastness tothermoflxing, washing, rubbing and light.

EXAMPLE 4 A fabric of poly-l,4-cyclohexane-dimethylene terephthalate isimpregnated at room temperature with a clear blue solution containing 10parts of a dyestuff of the formula Br 0 CH:

/CH: OaN -N=N N CZHAOCO-CPHCQ l CH: 1 N0: NHC OQH:

in 990 parts tetrachloroethylene.

After squeezing to a weight increase of 60%, the fabric is dried at 80Cfor 1 minute. The dyestuff is subsequently fixed by heating the fabricat 220C for 45 seconds. The small proportion of non-fixed dyestuff issubsequently washed out by a brief treatment in coldtetrachloroethylene. After drying, a blue dyeing is obtained, which ischaracterised by its high dyestuff yield, very good build-up andoutstanding fastness properties, especially very good fastness tothermofixing, washing, rubbing and light.

Dyeings of equally satisfactory fastness properties were obtained in theshades stated in the following Table on fabrics of polyester,triacetate, polyamidc, polyurethane or polyolefinc fibres when thedyestuff mentioned in Example 4 was replaced with the same amount of oneof the dyestuffs listed in the following Table.

Dyostull Slmdu Ruby.

Red-viuiet.

Orange.

Vlolul.

Rnd-urungn.

Red.

EXAMPLE 5 A fabric of polyethylene terephthalate fibres is impregnatedat room temperature with a clear red solution containing dyestuff isfixed by treating the fabric with overheated l,l,l-trichloroethanevapour at 140C for 45 seconds. The small proportion of non-fixeddyestuff is subsequently washed out by briefly rinsing in cold 1,1,1-

pal-ts f a d t ff f the f ul 5 trichloroethane. After drying, a clearviolet dyeing is obtained, which is characterised by its high dyestufi QQ yield, very good build-up and outstanding fastness OzN -N=N 1 1properties.

, a 10 EXAMPLE 7 i CH4OCO GHCH A fabric ofpoly-1,4-cyclohexane-dimethylene terei phthalate is impregnated at roomtemperature with a clear red solution containing 7 parts nonylphenolheptaethylene glycol ether in 10 parts of a dyestuff of the formula 983parts tetrachloroethylene. After squeezing to a weight increase of 60percent, the fabric is dried at 80C for 1 minute. The dyestuff issubsequently fixed by heating the fabric at 190 220C OzN N=N for 45seconds. The small proportion of non-fixed dyestuff is then washed outby briefly rinsing with cold tetrachloroethylene. After drying, a clearred dyeing is ob- (021140 0 O CHICH:CHiCHJ)Z tained, which ischaracterized by its high dyestuff yield, very good build-up andoutstanding fastness properties, especially very good fastness tothermofixing, washing, in 990 Parts tetrachloroethyl'eney rubbmg andhght' After squeezing to a weight increase of 60 percent, the EXAMPLE 6dyestuff is fixed by treating the fabric with overheated Itetrachloroethylene vapour at 150C for 35 seconds. A fabric ofpolyethylene terephthalate fibres is im- The Small proponion of norm-meddyestuff is tha pregnated at room temperature with a clear violetsoluwashed out by briefly rinsing in cold tetrachlorw tlon comammgethylene. After drying, a clear red dyeing is obtained, 10 Parts of adyestuff of the formula which is characterised by its high dyestuffyield, very good build-up and outstanding fastness properties. Br

0,13, Dyeings of equally satisfactory fastness properties O N--N:N wereObtained in the shades given in the following I C H Table on fabrics ofpolyester, tnacetate, polyamide, H JN V Ng coo m 3 polyurethane orpolyolefine fibres, when the dyestuff mentioned in Example 1 wasreplaced with the same in 990 parts l,l,1-trichloroethane. amount of oneof the dyestuffs listed in the following After squeezing to a weightincrease of 60 percent, the Table:

Dyestufl Shade 0] Yollowlsh-red.

| CH: O=N--N=NN CH CH OCO-+CH3) CH3 2 CN Red.

CH; 0nNN= N-N (cmcmo o 0c -cHa) CH: 2

Cl Yellow-brown.

CH: ozN--N=N -N(cmcmo CO-(iJ-CI-Ia) (I3 CH: 2

01 Red.

CHa OzN-N=N-N cmcmoco-a-cm) CH: 2

01 Rod.

03H: o=N-N=N' omcmo 00-011 02H 2 CN Blulsh-red.

OaN

ON OCH:

$1 CH CHzOCO-C (CH3):

CHICHIO COCH H5Ca0zS- N=N N\ CH CHaCH: O CHiCHl 0 C 0 (CHI) loCHa ShadeReddlsh blue.

Blue.

Orange.

Yellowish orange.

Red.

Reddlsh orange.

Orange.

TABLE-Continued CHzCHzO C (ii-(CH1) CH3 Shade Red.

Reddlsh brown.

EXAMPLE 8 A fabric of polyethylene terephthalate fibres is im-' dyestuffis fixed by treating the fabric with overheated l,l,l-trichloroethanevapour at 140C for 45 seconds. The small proportion of non-fixeddyestuff is subsequently washedout by briefly rinsing in cold 1,1,1-trichloroethane. After drying, a reddish navy-blue dyeing is obtained,which is characterised by its high dyestuff yield, very good build-upand outstanding fastness properties.

EXAMPLE 9 A fabric of cellulose triacetate fibres is impregnated at roomtemperature with a clear blue-violet solution containing 10 parts of theazo dyestuff 2,4-dinitro-6-bromoaniline4-(2-ethyl-hexanoylamino)-2-N-ethyl-N-[{3-(t-butylcarbonyloxy)-ethyl]-anisole and 7 parts nonylphenolheptaethylene glycol ether in 983 parts tetrachloroethylene.

After squeezing to a weight increase of 60 percent, the fabric is driedat 80C for l minute. The dyestuff is subsequently fixed by heating thefabric at 215C for 1 minute. A reddish navy-blue dyeing is obtained,which is characterised by its high dyestufi yield, very good build-upand outstanding fastness properties, especially very good fastness tothermofixing, washing, rubbing and light.

We claim:

1. Process for the continuous dyeing of synthetic polyester fibermaterial comprising the steps of A. impregnating the fiber material witha nonaqueous dyeing liquor said liquor consisting essentially of anorganic solvent and an azo dyestuff, said organic solvent consisting ofwater-immiscible halogenated hydrocarbon boiling between 40 and 150C,said azo dyestuff having the formula in which A is a carboorheterocyclic diazo component;

R is hydrogen, chlorine, bromine, methyl, methoxy or ethoxy;

R is hydrogen, chlorine, bromine, methyl, methoxy, ethoxy or acylaminoof the formula -NH--COR where R is C C -alkyl; cycloalkyl; benzyl;phenyl;

phenyl substituted by C,-C -alkyl; phenoxymethyl; acyloxymethyl withone-l8 carbon atoms in the acyl radical; methoxy-methyl; chloromethyl; C-C -alkoxy; or dialkylamino of one-l 8 carbon atoms;

-CH:CHO CO-Ro R, is C C, -alkyl; cycloalkyl; phenyl; phenyl substitutedby C C, -alkyl; benzyl; phenoxymethyl; benzyl or phenoxymethylsubstituted by C -C alkyl;

m is l or 2;

n is l, 2 or 3;

R is hydrogen; C -C -alkyl; benzyl or benzyl substituted by halogen, C-C -alkyl or C,-C -alkoxy; B-phenylethyl; B-cyanoethyl; B-methoxyethyl;B-ethoxyethyl; B-C -C -alkylsulfonylethyl; B-phenylsulfonylethyl orB-vinylsulfonylethyl; or R has the same meaning as R with the provisothat the total of carbon atoms in R R2, R3 and R4 is 6 t0 B. subjectingthe fiber material to a heat-treatment to fix said azo dyestuff on saidfiber.

2. The process of claim 1 in which the sum of carbon atoms in R R R andR is 10 to20.

3. The-process of claim 1 in which R is C C-,-alkyl.

4. The process of claim 1 in which R is heptyl-(3).

5. The process of claim 1 in which A is a phenyl radical of the formulain which R, is halogen, C,-C -alkyl, C,C -alkoxy,

C,-C -alkoxycarbonyl, cyclohexoxycarbonyl, trifluoromethyl, nitro,cyano, C,C -alkyIsulfonyl, phenyl-sulfonyl or C,-C dialkylaminosulfonyl;R is hydrogen, halogen or nitro; and R is hydrogen, halogen or cyano.

6. The processof claim 1 in which A is a substituted or unsubstitutedthiazole or a substituted or unsubstituted thiadiazole.

7. The process of claim 1 in which A is a thiazole radical of theformula 9. The process of claim 1 in which A is a thiadiazole radical ofthe formula in which R is C C -alkyl; phenyl, or substituted phenyl.

10. The process of claim 1 in which said azo dye-stuff is soluble insaid water-immiscible organic solvent.

11. The process of claim 10 in which the dyed material is subjected to asubsequent step of (C) rinsing with water-immiscible organic solvent inwhich said azo dyestuff is soluble.

12. The process of claim 1 in which said waterimmiscible organic solventis an aliphatic chlorohydrocarbon having a boiling point of between 40and C.

13. The process of claim 1 in which said waterimmiscible organic solventis selected from the group consisting of tetrachloroethylene,trichloroethylene, 1,1 l -trichloroethane and 1,1,l-trichloropropane.

14. The process of claim 1 in which said heattreatment is conducted withdry heat at l20230C.

15. The process of claim 1 in which said heat treatment is conductedwith solvent vapor at lOOl50C.

2. The process of claim 1 in which the sum of carbon atoms in R1, R2, R3and R4 is 10 to
 20. 3. The process of claim 1 in which R6 isC4-C7-alkyl.
 4. The process of claim 1 in which R6 is heptyl-(3).
 5. Theprocess of claim 1 in which A is a phenyl radical of the formula
 6. Theprocess of claim 1 in which A is a substituted or unsubstituted thiazoleor a substituted or unsubstituted thiadiazole.
 7. The process of claim 1in which A is a thiazole radical of the formula
 8. The process of claim1 in which A is a isothiazole radical of the formula
 9. The process ofclaim 1 in which A is a thiadiazole radical of the formula
 10. Theprocess of claim 1 in which said azo dye-stuff is soluble in saidwater-immiscible organic solvent.
 11. The process of claim 10 in whichthe dyed material is subjected to a subsequent step of (C) rinsing withwater-immiscible organic solvent in which said azo dyestuff is soluble.12. The process of claim 1 in which said water-immiscible organicsolvent is an aliphatic chlorohydrocarbon having a boiling point ofbetween 40* and 150*C.
 13. The process of claim 1 in which saidwater-immiscible organic solvent is selected from the group consistingof tetrachLoroethylene, trichloroethylene, 1,1,1-trichloroethane and1,1,1-trichloropropane.
 14. The process of claim 1 in which saidheat-treatment is conducted with dry heat at 120*-230*C.
 15. The processof claim 1 in which said heat treatment is conducted with solvent vaporat 100*-150*C.